500 Naturwissenschaften und Mathematik
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In international business relationships, such as international railway operations, large amounts of data can be exchanged among the parties involved. For the exchange of such data, a limited risk of being cheated by another party, e.g., by being provided with fake data, as well as reasonable cost and a foreseeable benefit, is expected. As the exchanged data can be used to make critical business decisions, there is a high incentive for one party to manipulate the data in its favor. To prevent this type of manipulation, mechanisms exist to ensure the integrity and authenticity of the data. In combination with a fair exchange protocol, it can be ensured that the integrity and authenticity of this data is maintained even when it is exchanged with another party. At the same time, such a protocol ensures that the exchange of data only takes place in conjunction with the agreed compensation, such as a payment, and that the payment is only made if the integrity and authenticity of the data is ensured as previously agreed. However, in order to be able to guarantee fairness, a fair exchange protocol must involve a trusted third party. To avoid fraud by a single centralized party acting as a trusted third party, current research proposes decentralizing the trusted third party, e.g., by using a distributed ledger based fair exchange protocol. However, for assessing the fairness of such an exchange, state-of-the-art approaches neglect costs arising for the parties conducting the fair exchange. This can result in a violation of the outlined expectation of reasonable cost, especially when distributed ledgers are involved, which are typically associated with non-negligible costs. Furthermore, the performance of typical distributed ledger-based fair exchange protocols is limited, posing an obstacle to widespread adoption.
To overcome the challenges, in this thesis, we introduce the foundation for a data exchange platform allowing for a fully decentralized fair data exchange with reasonable cost and performance. As a theoretical foundation, we introduce the concept of cost fairness, which considers cost for the fairness assessment by requesting that a party following the fair exchange protocol never suffers any unilateral disadvantages. We prove that cost fairness cannot be achieved using typical public distributed ledgers but requires customized distributed ledger instances, which usually lack complete decentralization. However, we show that the highest unilateral cost are caused by a grieving attack.
To allow fair data exchanges to be conducted with reasonable cost and performance, we introduce FairSCE, a distributed ledger-based fair exchange protocol using distributed ledger state channels and incorporating a mechanism to protect against grieving attacks, reducing the possible unilateral cost that have to be covered to a minimum. Based on our evaluation of FairSCE, the worst-case cost for data exchange, even in the presence of malicious parties, is known, which allows an estimate of the possible benefit and, thus, the preliminary estimate of economic utility. Furthermore, to allow for an unambiguous assessment of the correct data being transferred while still allowing for sensitive parts of the data to be masked, we introduce an approach for the hashing of hierarchically structured data, which can be used to ensure integrity and authenticity of the data being transferred.
Degenerative changes in the spine as well as back pain can be considered a common ailment. Incorrect loading of the lumbar spine structures is often considered as one of the factors that can accelerate degenerative processes, leading to back pain. For example, a degenerative change could be the occurrence of spinal stenosis following spondylolisthesis. Surgical treatment of spinal stenosis mainly focuses on decompressing the spinal canal with or without additional fusion through dorsal spondylodesis. There are differing opinions on whether fusion along with decompression provides potential benefits to patients or represents an overtreatment. Both conventional therapies and surgical methods aim to restore a “healthy” (or at least pain-free) distribution of load. Surprisingly little is known about the interindividual variability of load distribution in “healthy” lumbar spines. Since medical imaging does not provide information on internal forces, computer simulation of individual patients could be a tool to gain a set of new decision criteria for these cases. The advantage lies in calculating the internal load distribution, which is not feasible in in-vivo studies, as measurements of internal forces in living subjects are ethically and partially technically unfeasible. In the present research, the forward dynamic approach is used to calculate load distribution in multi-body models of individual lumbar spines. The work is structured into three parts: (I) Load distribution is quantified depending on the individual curvature of the lumbar spine. (II) Confidence intervals of the instantaneous center of rotation over time are determined, with which the motion behavior of healthy lumbar spines can be described. (III) Lastly, the effects of decompression surgeries on the load distribution of lumbar spines are determined.
Inland waters play an active role in the global carbon cycle. They collect carbon from upstream landmasses and transport it downstream until it finally reaches the ocean. Along this path, manifold processing steps are evident, resulting in (permanent) retention of carbon by sediment burial as well as loss by evasion to the atmosphere. Constraining these carbon fluxes and their anthropogenic perturbation is an urgent need. In this context, attention needs to be set on a widespread feature of inland waters: their partial desiccation. This results in the emergence of formerly inundated sediments to the atmosphere, referred to as dry inland waters. One observed feature of dry inland waters are disproportional high carbon dioxide (CO2) emissions. However, this observation was so far based on local case studies and knowledge on the global prevalence and fundamental mechanisms of these emissions is lacking. Against this background, this thesis aims to provide a better understanding of the magnitude and mechanisms of carbon emissions from dry inland waters on the global and local scale and to assess the impact of dry inland waters on the global carbon cycle. The specific research questions of this thesis were: (1) How do gaseous carbon emissions from dry inland waters integrate into the global carbon cycle and into global greenhouse gas (GHG) budgets? (2) What effect do seasonal and long term drying have on the carbon cycling of inland waters? The thesis revealed that dry inland waters emit disproportional large amounts of CO 2 on a global scale and that these emissions share common drivers across ecosystems. Quantifying global reservoir drawdown and upscaling carbon fluxes to the global scale suggests that reservoirs emit more carbon than they bury, challenging the current understanding of reservoirs as net carbon sinks. On the local scale, this thesis revealed that both, heterogeneous emission pattern between different habitats and seasonal variability of carbon emissions from the drawdown area, needs to be considered. Further, this thesis showed that re-mobilization of buried carbon upon permanent desiccation of water bodies can explain the observed emission rates, supporting the hypothesis of a positive feedback-loop between climate change and desiccation of inland waters. Overall, the present thesis highlights the importance of adding emissions from dry inland waters as a pathway to the global carbon cycle of inland waters.
Lakes and reservoirs are important sources of methane, a potent greenhouse gas. Although freshwaters cover only a small fraction of the global surface, their contribution to global methane emission is significant and this is expected to increase, as a positive feedback to climate warming and exacerbated eutrophication. Yet, global estimates of methane emission from freshwaters are often based on point measurements that are spatio-temporally biased. To better constrain the uncertainties in quantifying methane fluxes from inland waters, a closer examination of the processes transporting methane from sediment to atmosphere is necessary. Among these processes, ebullition (bubbling) is an important transport pathway and is a primary source of uncertainty in quantifying methane emissions from freshwaters. This thesis aims to improve our understanding of ebullition in freshwaters by studying the processes of methane bubble formation, storage and release in aquatic sediments. The laboratory experiments demonstrate that aquatic sediments can store up to ~20% (volumetric content) gas and the storage capacity varies with sediment properties. The methane produced is stored as gas bubbles in sediment with minimal ebullition until the storage capacity is reached. Once the sediment void spaces are created by gas bubble formation, they are stable and available for future bubble storage and transport. Controlled water level drawdown experiments showed that the amounts of gas released from the sediment scaled with the total volume of sediment gas storage and correlated linearly to the drop in hydrostatic pressure. It was hypothesized that not only the timing of ebullition is controlled by sediment gas storage, but also the spatial distribution of ebullition. A newly developed freeze corer, capable of characterizing sediment gas content under in situ environments, enabled the possibility to test the hypothesis in a large subtropical lake (Lake Kinneret, Israel). The results showed that gas content was variable both vertically and horizontally in the lake sediment. Sediment methane production rate and sediment characteristics could explain these variabilities. The spatial distribution of ebullition generally was in a good agreement with the horizontal distribution of depth-averaged (surface 1 m) sediment gas content. While discrepancies were found between sediment depth-integrated methane production and the snapshot ebullition rate, they were consistent in a long term (multiyear average). These findings provide a solid basis for the future development of a process-based ebullition model. By coupling a sediment transport model with a sediment diagenetic model, general patterns of ebullition hotspots can be predicted at a system level and the uncertainties in ebullition flux measurements can be better constrained both on long-term (months to years) and short-term (minutes to hours) scales.
With 47% land coverage in 2016, agricultural land was one of the largest terrestrial biomes in Germany. About 70% of the agricultural land was cropped area with associated pesticide applications. Agricultural land also represents an essential habitat for amphibians. Therefore, exposure of amphibians to agrochemicals, such as fertilizers and pesticides, seems likely. Pesticides can be highly toxic for amphibians, even a fraction of the original application rate may result in high amphibian mortality.
To evaluate the potential risk of pesticide exposure for amphibians, the temporal coincidence of amphibian presence on agricultural land and pesticide applications (N = 331) was analyzed for the fire-bellied toad (Bombina bombina), moor frog (Rana arvalis), spadefoot toad (Pelobates fuscus) and crested newt (Triturus cristatus) during spring migration. In 2007 and 2008, up to 80% of the migrating amphibians temporally coincided with pesticide applications in the study area of Müncheberg, about 50 km east of Berlin. Pesticide interception by plants ranged between 50 to 90% in winter cereals and 80 to 90% in winter rape. The highest coincidence was observed for the spadefoot toad, where 86.6% of the reproducing population was affected by a single pesticide in winter rape during stem elongation with 80% pesticide interception by plants. Late migrating species, such as the fire-bellied toad and the spadefoot toad, overlapped more with pesticide applications than early migrating species, such as the moor frog, did. Under favorable circumstances, the majority of early migrants may not coincide with the pesticide applications of arable fields during spring migration.
To evaluate the potential effect of pesticide applications on populations of the common frog (Rana temporaria), a landscape genetic study was conducted in the vinicultural area of Southern Palatinate. Due to small sample sizes at breeding sites within viniculture, several DNA sampling methods were tested. Furthermore, the novel repeated randomized selection of genotypes approach was developed to utilize genetic data from siblings for more reliable estimates of genetic parameters. Genetic analyses highlighted three of the breeding site populations located in viniculture as isolated from the meta-population. Genetic differentiation among breeding site populations in the viniculture (median pairwise FST=0.0215 at 2.34 km to 0.0987 at 2.39 km distance) was higher compared to genetic differentiation among breeding site populations in the Palatinate Forest (median pairwise FST=0.0041 at 5.39 km to 0.0159 at 9.40 km distance).
The presented studies add valuable information about the risk of pesticide exposure for amphibians in the terrestrial life stage and possible effects of agricultural land on amphibian meta-populations. To conserve endemic amphibian species and their (genetic) diversity in the long run, the risk assessment of pesticides and applied agricultural management measures need to be adjusted to protect amphibians adequately. In addition, other conservation measures such as the creation of new suitable breeding site should be considered to improve connectivity between breeding site populations and ensure the persistence of amphibians in the agricultural land.
Organic substances play an essential role for the formation of stable soil structures. In this context, their physico-chemical properties, interactions with mineral soil constituents and soil-water interactions are particu-larly important. However, the underlying mechanisms contributing to soil particle cementation by swollen or-ganic substances (hydrogels) remains unclear. Up to now, no mechanistic model is available which explains the mechanisms of interparticulate hydrogel swelling and its contribution to soil-water interactions and soil structur-al stability. This mainly results from the lack of appropriate testing methods to study hydrogel swelling in soil as well as from the difficulties of adapting available methods to the system soil/hydrogel.
In this thesis, 1H proton nuclear magnetic resonance (NMR) relaxometry was combined with various soil micro- and macrostructural stability testing methods in order to identify the contribution of hydrogel swelling-induced soil-water interactions to the structural stability of water-saturated and unsaturated soils. In the first part, the potentials and limitations of 1H NMR relaxometry to enlighten soil structural stabilization mechanism and vari-ous water populations were investigated. In the second part, 1H-NMR relaxometry was combined with rheologi-cal measurements of soil to assess the contribution of interparticulate hydrogel swelling and various polymer-clay interactions on soil-water interactions and soil structural stability in an isolated manner. Finally, the effects of various organic and mineral soil fractions on soil-water interactions and soil structural stability was assessed in more detail for a natural, agriculturally cultivated soil by soil density fractionation and on the basis of the experiences gained from the previous experiments.
The increased experiment complexity in the course of this thesis enabled to link physico-chemical properties of interparticulate hydrogel structures with soil structural stability on various scales. The established mechanistic model explains the contribution of interparticulate hydrogels to the structural stability of water-saturated and unsaturated soils: While swollen clay particles reduce soil structural stability by acting as lubricant between soil particles, interparticulate hydrogel structures increase soil structural stability by forming a flexible polymeric network which interconnects mineral particles more effectively than soil pore- or capillary water. It was appar-ent that soil structural stability increases with increasing viscosity of the interparticluate hydrogel in dependence on incubation time, soil texture, soil solution composition and external factors in terms of moisture dynamics and agricultural management practices. The stabilizing effect of interparticulate hydrogel structures further in-crease in the presence of clay particles which is attributed to additional polymer-clay interactions and the incor-poration of clay particles into the three-dimensional interparticulate hydrogel network. Furthermore, the simul-taneous swelling of clay particles and hydrogel structures results in the competition for water and thus in a mu-tual restriction of their swelling in the interparticle space. Thus, polymer-clay interactions not only increase the viscosity of the interparticulate hydrogel and thus its ability to stabilize soil structures but further reduce the swelling of clay particles and consequently their negative effects on soil structural stability. The knowledge on these underlying mechanisms enhance the knowledge on the formation of stable soil structures and enable to take appropriate management practices in order to maintain a sustainable soil structure. The additionally out-lined limitations and challenges of the mechanistic model should provide information on areas with optimization and research potential, respectively.
The work presented in this thesis investigated interactions of selected biophysical processes that affect zooplankton ecology at smaller scales. In this endeavour, the extent of changes in swimming behaviour and fluid disturbances produced by swimming Daphnia in response to changing physical environments were quantified. In the first research question addressed within this context, size and energetics of hydrodynamic trails produced by Daphnia swimming in non-stratified still waters were characterized and quantified as a function of organisms’ size and their swimming patterns.
The results revealed that neither size nor the swimming pattern of Daphnia affects the width of induced trails or dissipation rates. Nevertheless, as the size and swimming velocity of the organisms increased, trail volume increased in proportional to the cubic power of Reynolds number, and the biggest trail volume was about 500 times the body volume of the largest daphnids. Larger spatial extent of fluid perturbation and prolonged period to decay caused by bigger trail volumes would play a significant role in zooplankton ecology, e.g. increasing the risk of predation.
The study also found that increased trail volume brought about significantly enhanced total dissipated power at higher Reynolds number, and the magnitudes of total dissipated power observed varied in the range of (1.3-10)X10-9 W.
Furthermore, this study provided strong evidence that swimming speed of Daphnia and total dissipated power in Daphnia trails exceeded those of some other selected zooplankton species.
In recognizing turbulence as an intrinsic environmental perturbation in aquatic habitats, this thesis also examined the response of Daphnia to a range of turbulence flows, which correspond to turbu-lence levels that zooplankton generally encounter in their habitats. Results indicated that within the range of turbulent intensities to which the Daphnia are likely to be exposed in their natural habitats, increasing turbulence compelled the organisms to enhance their swimming activity and swim-ming speed. However, as the turbulence increased to extremely high values (10-4 m2s-3), Daphnia began to withdraw from their active swimming behaviour. Findings of this work also demonstrated that the threshold level of turbulence at which animals start to alleviate from largely active swimming is about 10-6 m2s-3. The study further illustrated that during the intermediate range of turbu-lence; 10-7 - 10-6 m2s-3, kinetic energy dissipation rates in the vicinity of the organisms is consistently one order of magnitude higher than that of the background turbulent flow.
Swarming, a common conspicuous behavioural trait observed in many zooplankton species, is considered to play a significant role in defining freshwater ecology of their habitats from food exploitation, mate encountering to avoiding predators through hydrodynamic flow structures produced by them, therefore, this thesis also investigated implications of Daphnia swarms at varied abundance & swarm densities on their swimming kinematics and induced flow field.
The results showed that Daphnia aggregated in swarms with swarm densities of (1.1-2.3)x103 L-1, which exceeded the abundance densities by two orders of magnitude (i.e. 1.7 - 6.7 L-1). The estimated swarm volume decreased from 52 cm3 to 6.5 cm3, and the mean neighbouring distance dropped from 9.9 to 6.4 body lengths. The findings of this work also showed that mean swimming trajectories were primarily horizontal concentric circles around the light source. Mean flow speeds found to be one order of magnitude lower than the corresponding swimming speeds of Daphnia. Furthermore, this study provided evidences that the flow fields produced by swarming Daphnia differed considerably between unidirectional vortex swarming and bidirectional swimming at low and high abundances respectively.
Agriculture covers one third of the world land area and has become a major source of water pollution due to its heavy reliance on chemical inputs, namely fertilisers and pesticides. Several thousands of tonnes of these chemicals are applied worldwide annually and partly reach freshwaters. Despite their widespread use and relatively unspecific modes of action, fungicides are the least studied group of pesticides. It remains unclear whether the taxonomic groups used in pesticide risk assessment are protective for non-target freshwater fungi. Fungi and bacteria are the main microbial decomposers converting allochthonous organic matter (litter) into a more nutritious food resource for leaf-shredding macroinvertebrates. This process of litter decomposition (LD) is central for aquatic ecosystem because it fuels local and downstream food webs with energy and nutrients. Effects of fungicides on decomposer communities and LD have been mainly analysed under laboratory conditions with limited representation of the multiple factors that may moderate effects in the field.
In this thesis a field study was conducted in a German vineyard area to characterise recurrent episodic exposure to fungicides in agricultural streams (chapter 2) and its effects on decomposer communities and LD (chapter 3). Additionally, potential interaction effects of nutrient enrichment and fungicides on decomposer communities and LD were analysed in a mesocosm experiment (chapter 4).
In the field study event-driven water sampling (EDS) and passive sampling with EmporeTM styrene-divinylbenzene reverse phase sulfonated disks (SDB disks) were used to assess exposure to 15 fungicides and 4 insecticides. A total of 17 streams were monitored during 4 rainfall events within the local application period of fungicides in 2012. EDS exceeded the time-weighted average concentrations provided by the SDB disks by a factor of 3, though high variability among compounds was observed. Most compounds were detected in more than half of the sites and mean and maximum peak (EDS) concentrations were under 1 and 3 µg/l, respectively. Besides, SDB disk-sampling rates and a free-software solution to derive sampling rates under time-variable exposure were provided.
Several biotic endpoints related to decomposers and LD were measured in the same sampling sites as the fungicide monitoring, coinciding with the major litter input period. Our results suggest that polar organic fungicides in streams change the structure of the fungal community. Causality of this finding was supported by a subsequent microcosm experiment. Whether other effects observed in the field study, such as reduced fungal biomass, increased bacterial density or reduced microbial LD can be attributed to fungicides remains speculative and requires further investigation. By contrast, neither the invertebrate LD nor in-situ measured gammarid feeding rates correlated with water-borne fungicide toxicity, but both were negatively associated with sediment copper concentrations. The mesocosm experiment showed that fungicides and nutrients affect microbial decomposers differently and that they can alter community structure, though longer experiments are needed to determine whether these changes may propagate to invertebrate communities and LD. Overall, further studies should include representative field surveys in terms of fungicide pollution and physical, chemical and biological conditions. This should be combined with experiments under controlled conditions to test for the causality of field observations.
Global crop production increased substantially in recent decades due to agricultural intensification and expansion and today agricultural areas occupy about 38% of Earth’s terrestrial surface - the largest use of land on the planet. However, current high-intensity agricultural practices fostered in the context of the Green Revolution led to serious consequences for the global environment. Pesticides, in particular, are highly biologically active substances that can threaten the ecological integrity of aquatic and terrestrial ecosystems. Although the global pesticide use increases steadily, our field-data based knowledge regarding exposure of non-target ecosystems such as surface waters is very restricted. Available studies have by now been limited to spatially restricted geographical areas or had rather specific objectives rendering the extrapolation to larger spatial scales questionable.
Consequently, this thesis evaluated based on four scientific publications the exposure, effects, and regulatory implications of particularly toxic insecticides` concentrations detected in global agricultural surface waters. FOCUS exposure modelling was used to characterise the highly specific insecticide exposure patterns and to analyse the resulting implications for both monitoring and risk assessment (publication I). Based on more than 200,000 scientific database entries, 838 peer-reviewed studies finally included, and more than 2,500 sites in 73 countries, the risks of agricultural insecticides to global surface waters were analysed by means of a comprehensive meta-analysis (publication II). This meta-analysis evaluated whether insecticide field concentrations exceed legally accepted regulatory threshold levels (RTLs) derived from official EU and US pesticide registration documents and, amongst others, how risks depend on insecticide development over time and stringency of environmental regulation. In addition, an in-depth analysis of the current EU pesticide regulations provided insights into the level of protection and field relevance of highly elaborated environmental regulatory risk assessment schemes (publications III and IV).
The results of this thesis show that insecticide surface water exposure is characterized by infrequent and highly transient concentration peaks of high ecotoxicological relevance. We thus argue in publication I that sampling based on regular intervals is inadequate for the detection of insecticide surface water concentrations and that traditional risk assessment concepts based on all insecticide concentrations including non-detects lead to severely biased results and critical underestimations of risks. Based on these considerations, publication II demonstrates that out of 11,300 measured insecticide concentrations (MICs; i.e., those actually detected and quantified), 52.4% (5,915 cases; 68.5%) exceeded the RTL for either water (RTLSW) or sediments. This indicates a substantial risk for the biological integrity of global water resources as additional analyses on pesticide effects in the field clearly evidence that the regional aquatic biodiversity is reduced by approximately 30% at pesticide concentrations equalling the RTLs. In addition, publication II shows that there is a complete lack of scientific monitoring data for ~90% of global cropland and that both the actual insecticide contamination of surface waters and the resulting ecological risks are most likely even greater due to, for example, inadequate sampling methods employed in the studies and the common occurrence of pesticide mixtures. A linear model analysis identified that RTLSW exceedances depend on the catchment size, sampling regime, sampling date, insecticide substance class, and stringency of countries` environmental regulations, as well as on the interactions of these factors. Importantly, the risks are significantly higher for newer-generation insecticides (i.e., pyrethroids) and are high even in countries with stringent environmental regulations. Regarding the latter, an analysis of the EU pesticide regulations revealed critical deficiencies and the lack of protectiveness and field-relevance for current presumed highly elaborated FOCUS exposure assessment (publication IV) and overall risk assessment schemes (publication III). Based on these findings, essential risk assessment amendments are proposed.
In essence, this thesis analyses the agriculture–environment linkages for pesticides at the global scale and it thereby contributes to a new research frontier in global ecotoxicology. The overall findings substantiate that agricultural insecticides are potential key drivers for the global freshwater biodiversity crisis and that the current regulatory risk assessment approaches for highly toxic anthropogenic chemicals fail to protect the global environment. This thesis provides an integrated view on the environmental side effects of global high-intensity agriculture and alerts that beside worldwide improvements to current pesticide regulations and agricultural pesticide application practices, the fundamental reformation of conventional agricultural systems is urgently needed to meet the twin challenges of providing sufficient food for a growing human population without destroying the ecological integrity of global ecosystems essential to human existence.
The increasing application of titanium dioxide nanoparticles (nTiO2) entails an increased risk regarding their release to surface water bodies, where they likely co-occur with other anthropogenic stressors, such as heavy metals. Their co-occurrence may lead to an adsorption of the metal ions onto the particles. These nanoparticles often sediment, due to their agglomeration, and thus pose a risk for pelagic or benthic species. The combined toxicity of nTiO2 and heavy metals is likely influenced by the properties of both stressors (since they may alter their interaction) and by environmental parameters (e.g., organic matter, pH, ionic strength) affecting their fate.
These issues were not yet systematically examined by the recent literature. Therefore, this thesis investigated the influence of nTiO2-products with differing crystalline phase composition on the toxicity of copper (as representative for heavy metals) in presence of different organic matters using the pelagic test organism Daphnia magna.
Moreover, the duration of the stressors` interaction (=aging) likely modulates the combined toxicity. Hence, the influence of nTiO2 on copper toxicity after aging as a function of environmental parameters (i.e., organic matter, pH, ionic strength) was additionally investigated.
Finally, the transferability of the major findings to benthic species was examined using Gammarus fossarum. The present thesis discovered a reduction of the copper toxicity facilitated by nTiO2 for all assessed scenarios, while its magnitude was determined by the surface area and structure of nTiO2, the quantity and quality of organic matter as well as the aging of both stressors. The general copper toxicity reduction by nTiO2 was also transferable to benthic species, despite their potentially increased exposure due to the sedimentation of nTiO2 with adsorbed copper. These observations suggest the application of nTiO2 as remediation agent, but potential side effects (e.g., chronic toxicity, reactive oxygen species formation) require further investigations. Moreover, questions regarding the transferability to other stressors (e.g., different heavy metals, organic chemicals) and the fate of stressors adsorbed to nTiO2 in aquatic ecosystems remain open.